DE2439007A1 - PROCESS FOR MANUFACTURING REFINING CATALYSTS AND THEIR USE FOR HYDROGENATION OF PETROLEUM FRACTIONS CONTAINING METAL AND ASPHALT - Google Patents

Description

BASF Aktiengesellschaft

Our sign; O.Z. 30 751 Vo / MW 6700 Ludwigshafen, August 8th, 1974

Process for the production of refining catalysts and their use for the hydrogenation of metal and petroleum fractions containing asphalt

The present invention relates to a process for the production of refining catalysts and their use in one Process for hydrated desulphurization of petroleum fractions. When using these catalysts, vacuum gas oils in particular can be used or residual oils from atmospheric distillation are treated under milder reaction conditions than in Use of conventional catalysts.

The hydrogenative desulphurization of crude oil residues is carried out by the asphaltenes and organometallic compounds they contain difficult. These cause deposits on the catalyst, which reduce the activity of the catalyst cause. In order to maintain a certain degree of desulphurisation, it is necessary with otherwise unchanged reaction conditions, to continuously increase the reaction temperature during operation (compare the figure). Elevated reaction temperatures but in turn accelerate the coke deposition on the catalyst, so that after relatively short operating times the Catalyst must either be regenerated or replaced. This makes the economic efficiency of processes for catalytic Desulfurization of e.g. vacuum gas oils or distillation residues greatly reduced.

Recently there are already catalysts with increased activity and service life has been developed. These catalysts have a certain pore structure. Give good results Catalysts, the cobalt or nickel together with molybdenum or tungsten on an AlpO -, - support stabilized by the addition of SiOp and their pores are mostly made up of micropores

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with diameters below 100 Å exist. For this purpose, in particular to the disclosed German applications 2 233 9 ^ 3 and 2 l60 7O4 referenced.

It has now been found that the activity and the service life for the desulfurization of vacuum gas oils and distillation residues Catalysts containing cobalt and / or nickel and molybdenum used can be further improved, if a ΑΙρΟ ,, carrier is used, the additional chromium oxide contains.

The present invention therefore relates to a process for the production of a refining catalyst, the cobalt and / or nickel together with molybdenum oxide as active catalyst components on aluminum oxide as a carrier. The method is characterized in that a carrier is used, which contains 3 to 15 weight percent chromium oxide.

The support of the catalyst prepared according to the invention consists of 85 to 97 percent by weight of aluminum oxide and contains 3 to 15 percent by weight of chromium oxide Aluminum oxide on chromium oxide finely suspended in water or by mixing freshly precipitated chromium oxide hydrate be made with alumina hydrate.

However, it is preferably produced as follows

The amount of a soluble chromium salt such as chromium sulfate or chromium alum required for the desired chromium content is added to an aqueous solution of aluminum sulfate, nitrate or chloride. A mixture of aluminum oxide and chromium oxide hydrates is precipitated from the solution of these two metal salts with a basic precipitant such as ammonia or an aqueous sodium aluminate solution, the precipitant and the solution being introduced into a precipitation vessel together with stirring. The precipitation is preferably carried out in a temperature range from 60 to 95 ^° C .; the cheapest pH

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The range for the precipitation is between 6.5 and 8.55, within this range, lower pH values are preferred at higher temperatures. The precipitate is filtered off and freed from sulfate and, if appropriate, sodium ions by washing; the filter cake can be dried in a tray dryer or drying cabinet at 120 to 150 ° C. until its water content is still about 50 to βθ % . Alternatively, the filter cake can also be dried to a residual water content of 20 to 30% by spray drying

again

However, the spray material can then / be set to a value between 40 and 50 % .

As active catalyst components, metal oxides of the 8th subgroup are used together with oxides of the 6th subgroup, Cobalt and / or nickel oxide are preferably used together with MoO. When using WO ,, instead of MoO ,, is the hydrogen consumption with the same degree of desulfurization a little bit higher.

For the hydrogenating desulfurization of vacuum gas oils or distillation residues, a content of 2.5 to 5 % of metal oxides of the 8th subgroup and a content of 5 to 13 percent by weight of metal oxides of β. Subgroup proved to be sufficient. Higher metal oxide contents cause practically no further increase in activity.

The active catalyst constituents can be used in a manner known per se either in the form of an ammoniacal nickel or Cobalt molybdate solution can be applied to the dried and calcined carrier by soaking. But also, if the production of extrusions is intended, added to the aluminum oxide / chromium oxide paste prior to the mixing process and kneaded together with this and water.

The catalyst according to the invention can be used quite generally for the refining of hydrocarbon fractions;

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it is preferably used for the desulphurisation of vacuum gas oils or residual oils from the atmosphere Crude oil distillation used «For this process, temperatures of 350 to 450 C, hydrogen partial pressures from 50 to 100 atmospheres, hydrogen / hydrocarbon ratios from 0.25 to 2 Nm hydrogen per kg of hydrocarbon and catalyst loadings of 0.5 to 1.5 kg Hydrocarbon applied per liter of catalyst per hour. The choice of reaction conditions within the above mentioned limits depends on the nature of the raw material and the desired degree of desulphurisation, oils with a high Asphalt and metal content are generally refined under more severe reaction conditions than oils with lower asphalt and metal content.

The invention is explained in more detail with reference to Examples 1 and 2 below. In Example 1, the production of a Catalyst A described according to the teaching of the invention. Example 2 contains a comparative experiment of the invention Catalyst A with a catalyst B from the prior art (DOS 2 233 9 ^ 3).

example 1

Preparation of Catalyst A According to the Invention:

^{A catalyst carrier} with a content of 5 and 95 % ^A1 2 ° 3 ^{wle fol} & t was produced:

67.8 g of anhydrous chromium sulfate (33 to 34 % Cr ₂ O 2) were dissolved with heating in 5560 ml of technical aluminum sulfate solution, 7% algae content. This solution was stirred into a precipitating flask together with a 25 percent ammonia solution to precipitate a precipitate. A temperature between 83 and 87 ^° C. and a pH value between 6.5 and 7 * 0 were maintained during the precipitation. After the precipitation process had ended, stirring was continued; then the precipitate was filtered off and washed with 0.25 # strength ammonium carbonate water to a residual content of 0.1 # sulfate.

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The filter cake was dried at 150 ° C. for 16 hours. 532 g of the filter cake dried in this way but still containing water (corresponding to 2βθ g dry matter) were mixed in a kneader with 53.5 g cobalt acetate and 43.1 g MoCU (corresponding to 5 % cobalt oxide / 13.5 % molybdenum oxide in the finished catalyst) deformed 1.5 mm extrudates and calcined for 4 hours at 500 ⁰ C after 12 hours of drying at 120 ⁰ C.

In the table, the composition and the physical data of catalyst A according to the invention are those of the catalyst B from the prior art (produced according to Example 1 of DOS 2 233 943). Also in the table is a catalyst C has been included, the support of which consists only of aluminum oxide. The carrier of the catalyst C was precipitated from aluminum sulfate solution, the active metals were pasted into the precipitate; this mass was spray dried, extruded and then calcined

Comparing the data in the table shows that the physical characteristics of the catalysts A, B and C are practical are the same, i.e. the improved desulfurization activity of the Catalyst A according to the invention is not due to a significantly improved pore structure, but to the addition from chromium oxide to the support of the catalyst.

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Tabel

A. B. C. Content of active metals in wt.% CoO
MoO 5
13.5 3.7
13.5 5
13.5 Composition of the vehicle Al ₂ O ₃
Cr ₂ O ₃
SiO ₂ 95
5 89
3.5 100 Physical data Bulk weight (g / l)
BCT surface area (m ² / g)
Total pore volume (ml / g)
mean pore radius in A 700
322
0.61
39.9 715
318
0.71
44.5 720
299
0.64
42.80 Proportion of pores with radii up to 40 8 (micro pores)
on the total pore volume in % 70.5 77.6 83.0 Pore volume of the micropores
with radii> 40 8 in ml / g o, i8 0.13 0.11

Example 2

The activity of the catalysts A, B and C shown in the table was tested with an atmospheric distillation residue from a Kirkukro oil. The distillation residue has
following properties:

Density (15 ° C) Sulfur content Asphalt content Conradson carbon

0.962 g / l 3.87 % 4.10 % 9.20 fo

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Metal content: 11 ppm iron 64 ppm Vanadium 25th ppm nickel

The activity test was carried out under the following test conditions: 100 atm total pressure, throughput 0.75 kg / oil / liter of catalyst and hour and a gas / oil ratio of 1.13 Nnr hydrogen per kg oil.

The temperature was gradually increased during the experiment so that an 80 to 85 percent desulfurization was maintained over the entire duration of the experiment. The temperature increase in ⁰ C (ordinate) necessary to maintain a constant desulfurization of 80 to 85 % is plotted in the figure for catalysts A, B and C as a function of the test duration in days (abscissa). At the end of the experiment, catalyst A according to the invention still has a temperature reserve of 15-18 'due to its higher desulfurization activity compared to catalysts B and C

C.

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Claims (3)

8 - ο.ζ. 30th Claims Γί. Process for the production of a refining catalyst which contains cobalt and / or nickel and molybdenum oxide as active catalyst components on aluminum oxide as a carrier, characterized in that a carrier is used which contains 3 to 15 percent by weight of chromium oxide. 2. The method according to claim 1, characterized in that the carrier is precipitated from an aqueous solution of the sulfates of aluminum and chromium at a temperature of 60 to 95 ° C and in a pH range of 6.5 to 8.5, optionally dries and calcined and then introduces the active metals in a manner known per se. 3. Use of the catalysts according to Claims 1 and 2 for hydrogenating desulphurisation of vacuum gas oils and distillation residues. BASF Corporation, Sign. «098 Q ¹ Q / Ό S 1 9